In the present work, a comparative study of LiF powders has been undertaken. Methods for the preparation of well-defined, high-purity LiF powders are reported. Sample characterization is carried out by combining transmission electron microscopy (TEM) with krypton gas adsorption isotherms. LiF crystallites obtained via precipitation in aqueous solutions are perfect regular cubes surrounded by {100} faces. However, fine particles produced by evaporation of LiF powders in an inert gas grow to more complicated polyhedra, surrounded by a predominant plane, which has been identified as a {111} plane.